Polymeric phosphates of copolymers of acyclic ethylenically unsaturated epoxy-free monomers and ethylenically unsaturated epoxy monomers



containing phosphoric acid ester groups.

United States Patent EPOXY-FREE MONOMERS AND ETHYLENI- CALLY UNSATURATEDEPOXY MONOMERS Martin E. Cupery, Wilmington, DeL, assignor to E. I. duPont de Nemours and Company, Wilmington, Dei., a corporation of DelawareNo Drawing. Application March 27, 1953, Serial N0. 345,233

20 Claims. (Cl. 260--85.7)

This invention relates to a new class of polymeric ma terials and totheir preparation. More particularly, this invention relates tocopolymers containing phosphoric acid ester groups, which copolymers aresoluble in organic solvents, and to coating compositions comprisingthese copolymers. a

This application is a continuation-in-part of my application, Serial No.218,885, filed April 2, 1951, and now abandoned.

The starting materials for the polymers of this invention are certaincopolymeric epoxides. ides are those polymers which contain Polymericepoxepoxy groups also called oxirane groups. A number of polymers ofthis type are known in the art, for example, polymers containingglycidyl groups,

CHr-CH--CH2 o It is an object of this invention to provide novelcopolymeric materials and a method for their preparation.

A further object is to provide a new class of copolymers A still furtherobject is to provide reaction products of epoxide copolymers withphosphoric acid, all of which are soluble in organic solvents, some ofwhich are soluble in aqueous alkaline solutions and others of which areinsoluble in such aqueous alkaline solutions. A further object is toprovide coating compositions comprising the new polymeric products ofthis invention as film-forming materials. Other objects will appearhereinafter.

The objects of this invention are accomplished by providing polymericphosphates which are the reaction products of a polymeric epoxidecopolymer and phosphoric acid in amount of at least about one-half moleper oxirane oxygen atom in said copolymer, said polymeric epoxidecopolymer having an epoxide oxygen content Within the range of 0.3 to 8%by weight and containing within the range of 3 to 60% by weight of apolymerized, ethylenically unsaturated epoxy monomer and within therange of 97 to 40% by weight of a polymerized, ethylenically unsaturatedacyclic epoxy-free monomer. These polymeric phosphates are soluble inorganic solvents and are useful as the film-forming ingredient incoating compositions.

The novel polymeric phosphoric acid esters of this invention can beobtained by reacting in an inert solvent and at a temperature below 100C., phosphoric acid with a polymeric epoxide which is a copolymer of apolymerizable ethylenically unsaturated epoxy compound with apolymerizable ethylenically unsaturated acyclic compound free from epoxygroups, said components being present in the copolymer in weight ratioof polymerized epoxy monomer to polymerized epoxy-free monomer withinthe range of 3:97 to 60:40, the phosphoric acid being used in amount ofat least about one-half mole per oxirane oxy- 2,723,971 Patented Nov.15, 1955 gen atom in said copolymer. Some of the products of thisinvention are alkali-soluble, and thus the invention also includes thesalts of the aforesaid polymeric phosphates and in particular theirwater-soluble alkali metal and ammonium salts including substitutedammonium salts.

The structure of the polymeric phosphates of this invention is not knownwith certainty but it is believed that in all cases these products arelinear, or substantially linear, polymers containing as lateralsubstituents phosphoric acid ester groups,

v ii oH resulting from the opening of the epoxy groups according to thefollowing scheme:

Analysis by electrometric titration with alkali indicates that there aretwo inflection points in the titration curve, demonstrating the presenceof essentially two acidic hydrogens per phosphate group in the polymer.Titrations using thymolphthalein as indicator give acidity values which,based on phosphate content, also indicate the presence of two acidichydrogen groups per phosphate group in the polymer.

The polymeric phosphates of this invention are conveniently prepared bytreating a solution of a polymeric epoxide of the type defined above atabout 20% solids in an inert solvent with phosphoric acid at atemperature in the range of 50 to C. for a period of one-half to threehours or at ordinary temperature of 2025 C. for longer periods of about1525 hours. As already stated, there should be used at least aboutone-half mole of phosphoric acid per-oxirane oxygen. Under suchconditions, little or no crosslinking takes place between the polymermolecules. Some of the products are soluble in aqueous alkali and insome cases are even soluble in Water. Partial or complete neutralizationof this type of polymeric phosphates with alkali hydroxides, ammonia oran amine, e. g., an alkylamine of 1 to 4 carbon atoms, gives the alkali,ammonium or substituted ammonium salts, which are water-soluble. Inother cases, the polymeric phosphates are insoluble in dilute aqueousalkali (which, for purposes of accuracy, is here defined as 5% aqueoussodium hydroxide). In all cases, however, the polymeric phosphates ofthis invention are soluble in organic solvents, e. g. acetone.

The factors responsible for the solubility or insolubility in aqueousalkali of the polymeric phosphates of this invention are of a complexnature. However, the principal factors appear to be the extent ofphosphation, i. e., the amount of -H2PO4 groups in the polymericphosphates, and the nature and composition of the starting copolymers.

The alkali-soluble polyphosphates are in general 0btained by startingwith a copolymer containing above about 3.9% by weight of oxiraneoxygen, and by reacting such copolymers with at least one mole ofphosphoric acid per oxirane group. This oxirane oxygen contentcorresponds by calculation to a phosphate content, calcu' lated as-H2PO4, of about 19% in the resulting polymeric phosphate.

The alkali-insoluble polyphosphates are in general obtained by reactingthe epoxy copolymers with phosphoric acid in amount, based on theoxirane oxygen, below that calculated to give about 19% H2PO4 in theresulting polyphosphate. This can be done by using copolymers containingless than about 3.9% oxirane oxygen and reacting such copolymers with atleast about: 0.5 mole of phosphoric acid per oxirane oxygen; or it canbe done by starting with a copolymer of higher oxirane oxygen contentthan about 3.9% and by reacting such proportion of the epoxy groups ofthe copolymer with phosphoric acid that the calculated -H2PO4 content ofthe resulting polyphosphate is less than about 19% by weight.

It will be at once apparent to the skilled chemist that the values forthe oxirane oxygen content and the corresponding calculated phosphatecontent as determining factors in alkali-solubility versus insolubilitycan vary somewhat from those given above because of the influence ofother factors such as the nature of the comonorners and of thecopolymers derived therefrom, the molecular weight of the copolymers,and the reaction conditions. For example, with respect to the epoxycornonomer, it has been found that glycidyl ether monomers, such asallyl glycidyl ester, react more readily with phosphoric acid thanglycidyl esters, such as glycidyl methacrylate. Variations are alsocaused by-the nature of the epoxy-free monomer.

It has been found that copolymers containing polymerized vinylcarboxylates, such as vinyl acetate, i. e., polymers containing acyloxygroups, form polyphosphates which deviate from the above-describedgeneral limitations with respect to the phosphatecontent required toimpart alkali solubility. Such polyphosphates have been found to besoluble in'alkali even at calculated phosphate contents well below 19%.This is also the case with polyphosphates of epoxide copolymers in whichthe epoxyfree component is a polymerized methacrylic acid ester of analcohol containing a water-solubilizing group such as an ether group, e.g., beta-methoxyethyl methacrylate.

The invention is illustrated in greater detail in the followingexamples, in which parts are by weight. The examples illustrate alsosome of the most important among the many uses of these polymers, viz.,their uses in coating compositions, as sizes for textile fibers and asagents in the treatment of leather.

Examples I-VI inclusive illustrate the preparation of alkali-solublepolyphosphates from epoxy copolymers in which the polymerized epoxy-freemonomer is free from acyloxy groups.

Example I A copolymer of allyl glycidyl ether and butyl methacrylate wasprepared by adding at a uniform rate over a period of aboutZ hours asolution of 852 parts of butyl methacrylate, 342 parts of allyl glycidylether and 36 parts of di-tertiary butyl peroxide to 1149 parts of allylglycidyl ether heated at 130 C. (12 C.) under nitrogen atmospheres.After the addition was completed, the polymerization mixture was heatedat 130-132 C. for an additional period of one hour. The unchangedmonomers were then removed by distillation under a pressure of 0.1-1 ofmercury while heating at about 100 C. There remained 1258 parts of apolymer which was soft and viscous at 100 C. This polymer containedabout 4% of oxirane oxygen (28% polymerized allyl glycidyl ether),corresponding to an oxirane equivalent weight of about 400, and it had amolecular weight of about 1900.

To a solution of 73 parts of this polymeric epoxide in 200 parts ofacetone was added 24 parts of 85 phosphoric acid (about 1.14 moles ofphosphoric acid per oxirane oxygen). The temperature increasedspontaneously to about 50 C. because of the heat of the exothermicreaction. The reaction was completed by heating the mixture at refluxtemperature (58 C.) for about one hour. The polymeric phosphateprecipitated from the solution upon addition of water but it dissolvedreadily in dilute ammonium hydroxide or sodium hydroxide, and could bereprecipitated from its alkaline solutions by acidification; A solutionof about 17% of this polymeric phosphate in dilute ammonium hydroxidegave on evaporation clear, transparent, hard, tough filmswhich aftercuring by heating at 120 C. for about 20 minutes.

were insoluble in water and unaffected by most organic solvents.

Example 11 A copolymer of glycidyl methacrylate and butyl methacrylatewas prepared by heating for 2 hours at C. a solution of 18 partsglycidyl methacrylate, 28.4 parts butyl methacrylate and 0.9 partbenzoyl peroxide in 110 parts dioxane. The conversion of monomer topolymer was over of theory. The copolymer contained 4.33% by weight ofoxirane oxygen, corresponding to 38.4% polymerized glycidylmethacrylate, and it had a molecular weight of about 4000.

Tea solution of 2 parts of 85% phosphoric acid in 8 parts of methylethyl ketone was added with stirring 5 parts of a 30% solution of theabove copolymer in dioxane (about 4.3 moles phosphoric acid per oxiraneoxygen). The solution was heated at 75 C. for one-half hour and thenpoured into about parts of water to precipitate the polymeric phosphate.After washing the precipitate with water to remove the excess phosphoricacid, the polymer was dissolved, with warming to 50 C., in 15 parts ofwater containing 1 part of concentrated ammonium hydroxide. Dilutesolutions (5% or lower) of this ammonium polyphosphate do notprecipitate upon addition of acetic acid to pH 4.5. Upon evaporation ofaqueous solutions of the ammonium salt, clear, colorless, hard, toughcoatings are obtained. Addition of aqueous solutions of inorganicaluminum and calcium salts to the ammonium polyphosphate solution givesprecipitates of aluminum and calcium polyphosphates.

Example 111 A copolymer of glycidyl methacrylate and methyl methacrylatewas prepared by heating 17.5 parts of glycidyl methacrylate, 32.5 partsof methyl methacrylate, 1 part of alpha,alpha-azodiisobutyronitrile andparts of acetone in a closed vessel for 16 hours at about 75 C. withmoderate agitation. Conversion of monomer to polymer was substantially100%. The copolymer contained 35% of polymerized glycidyl methacrylate,65% of polymerized methyl methacrylate and 3.94% of oxirane oxygen.

The polymer solution was diluted with acetone to give a solutioncontaining 25 parts of polymer solids and 100 parts of acetone. To thissolution were added 21.23 parts of aqueous orthophosphoric acid (85.4%H3PO4), corresponding to about 3' moles of phosphoric acid per oxiraneoxygen. The resulting mixture was heated in a closed vessel for 1 /2hours at about 60 C. with moderate agitation. A clear solution of thephosphate of the epoxide copolymer was thus produced. The polymericphosphate, containing approximately 19.3% of phosphate calculated as-H2PO4, was precipitated by adding the solution to 500 parts of water.The precipitate was separated by filtration and was washed twice with 50part portions of water. Then the precipitate was redissolved in acetone,reprecipitated with Water and filtered. Approximately lpart of the wetprecipitate was added to 100 parts of 5% aqueous sodium hydroxide and,in a separate test, to 100 parts of 5% aqueous ammonium hydroxide. Itwas soluble in both alkaline solutions. Although the re sultingsolutions were milky and not completely clear, they contained nofilterable solid matter.

Example IV A copolymer of glycidyl methacrylate and buty methacrylatewas prepared by the method described in Exof glycidyl methacrylate, 32.51 part of alpha,alpha'-azodiample III, using 17.5 parts parts ofibutylmethacrylate,

was substantially complete, giving a copolymer contain ing 35% ofpolymerized glycidyl methacrylate, 65% of polymerized butyl methacrylateand 3.94% of oxirane oxygen. This was treated as in Example III with14.15 parts of 85.4% phosphoric acid, corresponding to 1 mole ofphosphoric acid per oxirane oxygen. The polymeric phosphate, isolated asin Example III, was soluble in both 5% sodium hydroxide and 5% ammonium.hydroxide. The solutions were milky but did not contain any filterablesolid matter.

Example V A pressure vessel was charged with 840 parts of allyl glycidylether, 360 parts of vinyl chloride and 43 parts ofalpha,alpha-azodiisobutyronitrile. The vessel has heated at 80 C. for 16hours, then the unreacted vinyl chloride was distilled off and theresidual product was stripped of the unchanged allyl glycidyl ether bydistillation at 130l70 C. at 0.25 to 0.04 mm. mercury pressure. Thepolymeric epoxide thus obtained was a soft viscous material containing6.17% oxirane oxygen, corresponding to 44% polymerized allyl glycidylether, and having a molecular weight of about 1600.

To a solution of 40 parts of this polymeric epoxide in 160 parts ofdioxane was added 30 parts of 85% phosphoric acid (about 1.7 molesphosphoric acid per oxirane oxygen) and the homogeneous solution washeated at 70-90" C. for about 15 minutes. The resulting polymericphosphate was water soluble. It was precipitated by addition of free ofexcess phosphoric acid by repeated washings with 5% sodium chloridesolution. The final product was water soluble and its aqueous solutionscould be treated with basic reagents such as ammonia, amines or alkalimetal hydroxides to give weakly acidic, neutral. or basic solutions.Coatings obtained from aqueous solutions of this polymeric phosphatewere clear, hard, tough and had good adhesion to various substrates suchas metal or glass. Films of the ammonium salt'of this polymericphosphate became insoluble in water upon heating at 105-150 C.

Example VI A solution of 125 parts acrylonitrile, 125 parts allylglycidyl ether and parts of di-tertiary butyl peroxide was added at auniform rate over a period of about 2 hours to 250 parts of allylglycidyl ether held at a temperature of 120 to 145 C. in a closedvessel. When all was added the refluxing. was continued at about 138. C.for 1.5 hours. The polymerization mixture was freed of unchangedmonomers by heating at. 90 C. under less than 1.0 mm. mercury pressurefor about 4 hours. There remained 263 parts of a, slightly colored,soft, glassy solid which was soluble in acetone, dioxane, chloroform andcyclohexanone but was insoluble in xylene, butyl acetate and water.Based on monomers recovered, the copolymer contained about 54% by weightof allyl glycidyl ether and 46% by weight of acrylonitrile.

To a solution of 3 parts of the above copolymer dissolved in 12 parts ofdioxane was added 3 parts of 85% orthophosphoric acid (about 1.84 molesof phosphoric acid per oxirane oxygen). The solution was heated at 75 C.for one hour. The product so obtained was soluble in water butcoagulated from the aqueous solution upon the addition of sodiumchloride. After washing three times with 5% aqueous sodium chloride theresidual polymer was dissolved in water containing a low amount ofammonia. Upon evaporation on glass plates, such aqueous solutions gavefilms which were clear, hard and tough, and had excellent adhesion.

Examples VII-XII inclusive illustrate the preparation ofalkali-insoluble polyphosphates.

Example VII 7 A copolymer of glycidyl methacrylate and methylmethacrylate was prepared by heating 15.0 parts of glycaqueous sodiumchloride and was washed 6 idyl methacrylate monomer, 35.0 parts ofmethyl methacrylate monomer and 1 part ofalpha,alpha'-azodiisobutyronitril'e in 100- parts of acetone in a.closed vessel for 16 hours at about 75 C; with moderate agitation.Conversion of monomer to polymer was substantially 100%. The copolymercontained 3.38% by weight of oxirane oxygen, corresponding to 30%polymerized glycidyl methacrylate and 70% polymerized methylmethacrylate.

To 1 50 parts of the above-prepared solution (containing 50 parts ofepoxide copolymer) were added 12.12 parts of aqueous orthophosphoricacid (85.4% H3PO4). The resulting mixture was heated in a closed vesselfor 1% hours at about 60 C. with moderate agitation. The proportionswere equivalent to 1 mol. of HsPO4 for each mol' of oxirane oxygen. Aclear solution of the phosphate of the epoxide copolymer was thusproduced. The polymeric phosphate, containing approximately 17% ofphosphate calculated as -H2PO4, was precipitated by adding the solutionto 500 cc. of water. The precipitate was separated by filtration and waswashed twice with 50 cc. portions of water. Then the precipitate wasredissolved in acetone, reprecipitated with water and filtered.Approximately 1 part of the thus-produced wet precipitate was added to100 parts of a 5% ammonium hydroxide solution in water. The precipitatedid not dissolve even when stirred and heated at C. for 5 minutes. Theprecipitate was similarly insoluble in 5% sodium hydroxide.

A clear coating composition was prepared in the form of a 30% solutionof the copolymeric phosphate of this example in acetone. A thin coatingof this solution was poured on a clean steel panel which was then bakedfor 45 minutes at 280 F. A clear hard film resulted, which protected themetal from rusting.

A pigmented enamel was prepared by grinding in a ball mill until asmooth dispersion was obtained, 125 parts of the copolymeric phosphate,251 parts of methyl isobutyl ketone, 35 parts of butyl alcohol, parts ofethylene glycol monoethyl ether acetate and 100 parts of titaniumdioxide pigment. The resulting enamel was sprayed on a clean metal panelwhich was baked for 30 minutes at. 300 F. There resulted a durable whiteglossy coating which protected the metal substrate from rusting. Anenamel of these. properties is useful for finishing electricalappliances, outdoor furniture, and a wide variety of metal and ceramicarticles. Although baking or curing at high temperatures imparts themost useful properties to coatings prepared from the products of thisinvention, baking is not essential. Coatings may be dried in the air andtherefore may be used on substrates which will not withstand a largeamount of heat such as wood, organic fabrics and leather.

Example VIII The process of Example VII was repeated in all respectsexcept for the proportions of glycidyl methacrylate monomer and methylmethacrylate monomer, the composition of the resulting copolymer, andthe proportion of orthophosphoric acid, which were as follows:

The polymeric phosphates prepared in VIII-A, VIII-B and VIII-C of thisexample were insoluble in 5% ammonium hydroxide and 5% sodium hydroxide,as was the product of Example VII.

7 Example IX An epoxide copolymer containing 35% of polymerized glycidylmethacrylate, 65% of polymerized methyl methacrylate and 3.94% ofoxirane oxygen was prepared as in Example VII from 17.5 parts ofglycidyl methacrylate, 32.5 parts ofmethyl methacrylate, 1 part ofalpha,alpha'- azodiisobutyronitrile and 120 parts of acetone.

Treatment of the resulting copolymer solution with 14.15 parts of 85.4%phosphoric acid (1 mole of H3PO4 per mole of oxirane oxygen) by themethod of Example VII produced a gelled system. This result appeared tohave been caused by too high a concentration of the copolymer in thesolution.

Therefore, a less concentrated solution of the copolymer (25 partscopolymer solids, 225 parts acetone) was treated, by the method ofExample VII, with 5.65 parts of 85.4% phosphoric acid. This correspondsto 0.8 mole of phosphoric acid per oxirane oxygen. A clear solution ofthe polymeric phosphate resulted. The polymeric material was isolated asin Example VII. Approximately 1 part of the thus-produced wetprecipitate was insoluble in 100 parts of both 5% aqueous ammoniumhydroxide and 5% aqueous sodium hydroxide.

Example X X-A X-B Cornonomer charge (parts):

Glycidyl methacrylate 12. 5 15. Butyl Inethacrylate 37. 35. 0 Alpha,alpha azodiisobntyronitrile 1. 0 1.0 Aceto e 120 120 opolymercomposition (percent Glycidyl methacrylate. 25 30 Butyl methacrylate 7570 Oxirane oxygen 2. 82 3. 38 85.4% H3PO4 (parts) 10. 12. 10 Mols H3P04per mol of oxirane oxygen 1 1 Percent phosphate (as H2PO4) in polymericphosphate 14. 5 17. 0

Both of the polymeric phosphate products of X-A and XB of this examplewere insoluble in both 5% aqueous ammonium hydroxide and 5% aqueoussodium hydroxide.

. Example Xl acrylate was prepared as follows:

Portion A: Parts Allyl glycidyl ether monomer 642 Portion B:

Allyl glycidyl ether monomer 258 Methyl methacrylate monomer 600 Benzoylperoxide l6 Portion A was placed in a closed reaction vessel equippedwith an agitator, reflux condenser and thermometer and was heated toabout 130 C. Portion B was then added slowly at a constant rate duringthe ensuing 3 /2 hours while the temperature was maintained at about 130C. After all of Portion B had been added, the batch was held at thistemperature for an additional minutes. The unreacted monomers were thenremoved by distillation. 7

Approximately 50% of the starting monomers were thus converted to acopolymer containing approximately 20% of polymerized allyl glycidylether and 80% of polymerized methyl methacrylate. The oxirane oxygencontent of the copolymer was approximately 2.81%. The copolymer wasdissolved in 750 parts of methyl ethyl ketone to'produce a clearsolution having a 50% solids content. p p a A polyphosphate of the abovedescribed copolymer was for one hour.

prepared by reacting 750 parts of the 50% solution with 75.5 parts ofaqueous 85.4% H3PO4 in 500 parts of acetone at 60-70 C. for 1 hour withmoderate agitation. The proportions of copolymer and phosphoric acidwere equivalent to one mol of H3PO4 for each mol of oxirane oxygen. Aclear solution resulted in which the polymeric phosphate containedapproximately 14.5% of I -I2PO4. The polymeric material was separated byprecipitation, filtration and washing as in Example 1. Approximately onepart of the wet precipitate was added to 100 parts each of 5% ammoniumhydroxide and 5% sodium hydroxide and was found to be insoluble in bothmedia.

Example XII A copolymer of allyl glycidyl ether and vinyl chloride wasprepared by reacting 630 parts of allyl glycidyl ether monomer, 1470parts of vinyl chloride monomer and 21 parts of alpha,alpha-azodiisobutyronitrile in 922 parts of benzene in an agitatedautoclave at about 60 C. for 18 hours under an autogenous pressure of6070 pounds per square inch gauge.

Approximately 30% of the starting monomers were thus converted to acopolymer containing approximately 21% of polymerized allyl glycidylether and approximately 79% of polymerized vinyl chloride. The oxiranecontent of the copolymer was approximately 2.95%.

The polymeric material was separated by adding approximately 3 volumesof methyl'alcohol for each volume of copolymer solution and filtering.The precipitate was dissolved in acetone, reprecipitated in methylalcohol, filtered and dried.

A polyphosphate of the above described copolymer was prepared byreacting 300 parts of solid copolymer with 61 parts of aqueous 85 .4%H3PO4 in 555 parts of acetone at 60-70 C. for l'hour with moderateagitation. The proportions of copolymer and phosphoric acid wereequivalent to 1 mol of H3PO4 for each mol of oxirane oxygen. A clearsolution resulted, in which the polymeric phosphate containedapproximately 15.2% of H2PO4.

A portion of the polymeric phosphate solution was evaporated to drynessat room temperature. One part of the dry material was stirred into 100parts of 5% sodium hydroxide, but it did not dissolve. The solidmaterial was similarly insoluble in 5% ammonium hydroxide even at 6070C. Furthermore, when a portion of the acetone solution of the polymericphosphate was added to a mixture of equal parts of acetone and 5% sodiumhydroxide, the solid material precipitated and was insoluble in themedium.

Examples XIIIXVI inclusive illustrate the preparation of alkali-solublepolyphosphates from epoxy copolymers in which the polymerized epoxy-freemonomer contains acyloxy groups. It will be seen that alkali-solublepolyphosphates are obtained even when the oxirane oxygen content of thecopolymer is very low.

Example XIII A copolymer of allyl glycidyl ether and vinyl acetate wasprepared by warming to reflux temperature a solution of 18 parts ofbenzoyl peroxide in a mixture of 114 parts of allyl glycidyl ether and430 parts of vinyl acetate. When refluxing had started, heating wasdiscontinued and the solution was kept refluxing by the heat of theexothermic polymerization. Cooling was applied as required to controlthe reflux. When refluxing finally subsided, after about one-half hour,heating was again applied gradually to maintain a solution temperatureof -85 C. The unchanged monomers were removed by distillation underpressure of 0.11 mm. of mercury .while warming the polymer to 80-100 C.There was obtained 437 parts of a polymeric epoxide having an oxiraneoxygen content of 2.77%, corresponding to an oxirane equivalent weightof about 577 and to 20% of polymerized allyl glycidyl ether.

A solution .of. 10.4 parts of this polymeric epoxide in 30 parts ofdioxane was treated with 3 parts of phosphoric acid (1.45 moles ofphosphoric acid per oxirane oxygen) and the mixture was heated at 80 85.C. for 20 minutes. The polymeric pho'zphate so obtained precipitated bythe addition ofwatr but dissolved readily in dilute ammonium hydroxide.Such a solution had a viscosity of about 0.5 poiscs at 25% solidscontent. Evaporation of thin layers of this solution produced smooth,colorless, glossy, transparent, hard films which had exceptionally goodstrength, adhesion and toughness. Curing by heating at 110l50 C. causedinsolubiliz'ation.

The polymeric phosphate of this example was tested for textile size asfollows: A 10% aqueous solution of the ammonium salt of the polymericphosphate prepared as described above was obtained by addingportion-wise, with stirring, about 5 parts of concentrated ammoniumhydroxide to 1000 parts of an aqueous slurry containing 9.8% of.polyphosphate solids. The polyphosphate dissolved yielding a clearcolorless solution of pH 2.9 containing of polymeric phosphate ammoniumsalt. This solution was applied to a 70 denier, 34 filament yarn ofpolyethylene terephthalate, this yarn having a twist of 72 turns/in, andthe yarn so treated was dried on a steamheated cylinder. The treatedyarn was then used in a standard loom to weave a taffeta fabric of 135ends of yarn per inch and about 85 filling picks per inch. When the loomwas operated continuously for a period of 2 hours, no breaks orirregularities appeared in the warp. In larger scale tests, this andother polymeric phosphates prepared according to this invention showedexcellent yarn protection and adhesion 'in fabric Weaving, being clearlysuperior to conventional sizing materials such as gelatin, starch, andvarious commercial synthetic sizes.

Example XI V A solution of 6.8 parts of benZoyl peroxide in a mixture of205 parts of vinyl acetate, 22.8 parts of allyl glycidyl ether and 11.3parts of isopropanol was heated at 75 C. At this point heating wasdiscontinued, allowing the solution to reflux gently from the heat ofthe exothermic polymerization. The solution temperature at reflux slowlyincreased over a period of aboutone hour to 8789 C., while cooling wasapplied at intervals to avoid an excessive rate of refluxing and toorapid an increase in the solution temperature. After about one andone-half hours, moderate heating was applied to maintain a solutiontemperature of 85-87" C. At this stage, 11.3 parts. of isopropanol wasadded and'heating was continued for one hour at a solution temperatureof 85-87 C. An addition portion of 22.6 parts of isopropanol was addedand the heating was increased, allowing the low boiling fractionstodistill oil through a distillation column. Distillation was continuedfor about 2 hours, collecting 48.1 parts of distillate. At this pointthe viscous residue contained 86.4% of nonvolatile solids. .Analysiscopolymcr showed that it had an oxirane oxygen content of 1.31%,corresponding to 9.3% polymerized allyl glycidyl ether and a molecularweight of 3800.

To 260 parts of the 86.4% solution of polymeric epoxide described abovewas added at 40 C. a solution of 200 parts of 85% phosphoric acid in 200parts of isopropanol (9.3 moles of phosphoric acid per oxirane oxygen).The reaction mixture was well mixed while cooling to reduce the heat ofreaction. After allowing the mixture to stand for about hours. at 35-40"C., it was poured into six times its volume of water. The polymericphosphate which precipitated was separated from the water by decantationand washed twice with water. A sample, purified by dissolving in acetoneand again precipitating in water was dried with warming at 40C. underreduced pressure of .1 mm. mercury. A potentiometric titration showedfairly sharp inflection points, at pH 4.4 and 10.2, on a graph plottingalkali consumed versus pH of solution; The precipitated acidpolyphosphate was dissolved by adding about 560 parts of an isolatedsample of this 5 of water containing about 10 parts of added concerttrated ammonium hydroxide. There was thus obtained a solution of theammonium salt of this. polymeric phosphate containing 19% solids andhaving a pH of 5.85. Upon evaporation this solution formed clear,colorless, hard, moderately tough films. These films had excellentadhesive properties to wood, paper, metals and plastic substrates.

The usefulness of polymeric phosphates in the treatment of leather wasshown by the following experiments: Chromium tanned kidskin, washed freeof chromium salts with water, was drummed with about 3% by weight ofNeatsfoot oil emulsion at -55 C. for one-half hour. To the drum was thenadded enough of the above described 19% solution 0f ammoniumpolyphos'phate to give 45% by weight of the polymer phosphate salt basedon the dry weight of the kidskin, and. the drumming continued for 1 hourat 52-55 C. The treated skins were drained at 100% relative humidity for20 hours, passed through rubber squeeze rolls to remove excess moistureand dried at 55 C. for about 2 hours. The treated leather had aphosphorus content (calculated as P205) of 1.2% compared to 0.5% for acontrol leather treated identically except that the polymeric phosphatetreatment was omitted. The polymeric phosphate'treated leather hadexcellent body and hand and could readily be buffed to an excellentsuede finish. Lower concentrations of polyphosphates, e. g., 5% and 10%based on the dry weight of kidskin, likewise produced good plumping andbodying effects.

In another experiment, tanned cowhide. was swelled in dilute boraxsolution and treated with alum, followed by rinsing in water and by atreatment as above with the same 19% solution of ammonium polyphosphate,used in such an amount as to apply about 15% of polymer solids based onthe dry weight of the leather. After drying, the treated leather hadgreatly improved body and hand as compared to a control sample nottreated with the polyphosphate solution.

Example XV A solution comprising 950 parts of vinyl acetate, 50 parts ofallyl glycidyl ether, 150 parts' of dioxane and 10 parts of benzoylperoxide was heated with agitation to 73 C., at which temperature itrefluxed rapidly. The heating was discontinued and the solution allowedto reflux slowly under the heat of the exothermic polymerizationreaction. After about 20 minutes, the solution temperature reached 87 C.At this point, 150 parts of dioxane was added over a period of about 2minutes, lowering the solution temperature to 84 C. After about 10minutes the solution temperature reached 89 C. and foaming of theviscous solution was noted. Upon addition of 79 parts of isopropanol,the foaming subsided and the solution temperature was lowered to aboutC. The temperature then began to decrease and slight heating was appliedover a period of one and one-half hours to maintain a solutiontemperature of 80-95" C. At this point the solution contained 68%polymer solids, indicating about 94% conversion of monomers tocopolymer. To this viscous mass was added 211 parts of dioxane. Uponheating with stirring 100 parts of liquid containing 29.3% vinyl acetatewas distilled from the polymerization solution. The final solution ofthe copolymer contained 64% solids and had a. viscosity of about 200poises. The polymeric epoxide contained 0.62% of oxirane oxygen,corresponding to 4.4% polymerized allyl glycidyl ether, and it had amolecular weight of 7000.

To 781 parts of the above described polymeric cpoxide solutioncontaining 64% solids was added a solution of 220 parts of phosphoricacid in 220 parts of isopropanol (9.8 moles of phosphoric acid peroxirane oxygen). The solution, which warmed spontaneously to 3040 C.,was heated to 85 C. and then allowed to stand for several hours. Thepolymeric phosphate was precipitated by pouring into water and it waswashed thoroughly with water to remove excess phosphoric acid andsolvents. This polymer was completely soluble in water upon the additionof basic reagents such as ammonia, amines, such as diethylamine,triethylamine, trimethylamine, isopropylamine and ethanolamine, andalkali metal hydroxides, such as sodium and potassium hydroxide, and itwas reprecipitated from such solutions by addition of acid. Thepolyepoxidephosphoric acid reaction product had a neutralizationequivalent to about 870 and contained 1.76% phosphorus. A solution ofthe ammonium salts of this polymer had a viscosity of 0.03 poise at 13%solids and a pH of 9.1. Films evaporated from this solution and airdried were colorless, clear, hard and had excellent toughness.

Example XVI A mixture of 90 parts of vinyl acetate, 10 parts of 4- vinylcyclohexene oxide (B. P. 50-52 C./8-9 mm.) and 4 parts of benzoylperoxide was heated at refluxing temperature (73-78" C.) for about 3hours. The highly viscous polymerization mixture was dissolved in 200parts acetone and the polymer was precipitated by addition ofcyclohexane. It was again dissolved in acetone and reprecipitated byadding petroleum ether. The viscous resin was dissolved in a littlebenzene and the solvents then evaporated at reduced pressure of 1 to 0.1mm. mercury with warming at 50 C. The colorless, brittle solid polymercontained 0.74% oxirane oxygen, corresponding to 5.7% 4-vinylcyclohexene oxide content.

To a 15% solution of the above copolymer in dioxane was added an equalweight of a 15 solution of orthophosphoric acid in dioxane (about 18moles of phosphoric acid per oxirane oxygen). The homogeneous clearcomposition washeated at 7 80 C. for one hour. Upon adding this solutionto water, the insoluble polymeric phosphate was precipitated. It wasreadily washed with water to remove excess phosphoric acid. The purifiedproduct was highly soluble in dilute sodium hydroxide and ammoniumhydroxide. Films obtained from such solutions by evaporation were clear,colorless, smooth, glossy and hard.

As startingjmaterial in the preparation of the polymeric phosphates ofthis invention there can be used any polymeric epoxide which is acopolymer of a polymerizable, ethylenically unsaturated epoxy compoundwith a polymerizable, ethylenically unsaturated acyclic compound freefrom epoxy groups and in which the weight ratio of polymerized epoxycompound to polymerized oxiranefree unsaturate is within the range of3:97 to 60:40. Such copolymers ofler a number of important technicaladvantages in the preparation of polymeric phosphates. In

the first place, it is possible with their use to obtain polymericphosphates of high molecular weight, and moreover, the molecular weightis controllable to a large extent since the starting copolymers are madeby freeradical initiated addition polymerization according to methodswell understood in the art. In the second place, copolymers' of the typedefined above can be obtained which combine high molecular weight with awide range of oxirane oxygen content, a combination which is notobtained with epoxy polymers prepared by condensation 'reactions, suchas epoxy containing polymeric ethers. By properly selecting the weightratios of the comonomers and the polymerization conditions,'it ispossible to prepare copolymers containing various amounts of the epoxycontent, up to the limit (60% by weight) which has been found desirablefor reasons discussed below. In the third place, the starting copolymersare in general easy to prepare by well known methods and, in many cases,they otter substantial economic. advantages since the bulk of the weightcan be derived from a cheap, readily available polymerizable monomer.

The stated limits for the weight ratio of polymerized components in thestarting copolymers are critical. It

. 12, there is'appreciably less than 3% of polymerized epoxy compoundbased on the weight of total polymerized materials, there will not beenough epoxy groups present to react effectively with the phosphoricacid. On the other hand, if the polymerizable epoxy compound is presentin the polymerization mixture in proportions such that the resultingcopolymer has appreciably more than 60% of polymerized epoxy compoundbased on the total weight of polymerizable materials, then thepolymerization becomes difiicult to carry out and control sinceunsaturated epoxy monomers do not polymerize well per se. Furthermore,the above-mentioned economic advantages are substantially lessened.

Another way of expressing the chemical composition of the suitablecopolymers from which the polymeric phosphates are prepared is in termsof oxirane oxygen content. To obtain polyphosphates having a phosphatecontent sufficient to impart appreciably difierent properties, thepolymeric epoxide should contain at least 0.3% by weight of oxiraneoxygen. Preferably, the polymeric epoxide contains at least 0.6% byweight of oxirane oxygen. The upper limit of oxirane oxygen contentsuitable to give useful, economical polymeric phosphates has been foundto be about 8% by weight, and preferably 7%.

Another way of expressing these figures is in terms of oxiraneequivalent weight, that is, the molecular weight corresponding to oneatom of oxirane oxygen. It will be seen that 0.3% by weight of oxiraneoxygen corresponds to an oxirane equivalent weight of about 5300, whichis the upper limit for the suitable polymeric epoxides. Preferably, theoxirane equivalent weight is less than 2500 for polyepoxides havingmolecular weights of about 5000 to 7500. The properties of thepolyphosphates, however, also depend upon the composition of the epoxidepolymer as well as upon its molecular weight. The molecular weight ofthe starting polymeric epoxide preferably ranges between about 1500 andabout 10,000 but it can be as high as 50,000 or even higher. In general,if the molecular weight is high, it is preferred that the oxiraneequivalent weight be low, e. g., 300 to 500. If the molecular weight islow, for example, 15007000, the oxirane equivalent weight may besomewhat higher, for example, between 1000 and 2500, depending upon thecomposition of the copolymer. In general, the copolymer contains atleast 1.5 epoxy groups per molecule.

The epoxide copolymers are prepared by free radicalinitiatedpolymerization according to known methods and with known freeradical-producing initiators. It is of course important to avoidconditions which would tend to open or otherwise destroy the epoxygroups, such as the presence of strong acids. In order to producecopolymers of the desired composition, the monomers are in general usedin relative amounts within the range of 5 to parts of oxirane-containingunsaturate for to 25 parts oxirane-free unsaturate. Two or morecomonomers of each type may be used provided the above ratios areobserved.

A number of epoxide copolymers have been shown in the examples. Othersuitable starting materials include the copolymers of otherethylenically unsaturated epoxy compounds such as butadiene monoepoxide,glycidyl acrylate, vinyl glycidyl phthalate, allyl glycidyl maleate,allyl glycidyl phthalate, and the like with various acyclic vinylidenemonomers such as vinyl acetate, methyl acrylate, ethyl acrylate, methylmethacrylate, acrylamide, methacrylarnide, acrylonitrile,methacrylonitrile, 1,3- butadiene, isoprene, 2-chloro-1,3-butadiene,vinyl chloride, vinyl fluoride, isopropenyl acetate, vinylidenechloride, methyl vinyl ether, acrolein, methyl vinyl ketone, and thelike.

The preferred copolymers are made from monomers having only oneethylenic, carbon to carbon double bond, to minimize the danger ofcross-linking to insoluble materials. For best results and maximumfreedom from side reaction during the subsequent esterification, thecoatoms, and more particularly methyl baking temperatures than thepolymers should be free from groups, other than epoxy groups, which arereadily reactive with phosphoric acid, such as amino, hydroxyl, mercaptogroups and the like.

The preferred starting materials, because they give the most generallyuseful polymeric phosphates, are the copolymers of unsaturated epoxycompounds with polymerizable acyclic vinylidene compounds, i. e.,acyclic compound having a terminal methylene group attached through adouble bond to the adjacent carbon atom. These preferred materialsinclude the copolymers of unsaturated epoxy compounds with the vinylhalides, e. g., vinyl chloride, vinyl fluoride; the vinyl esters ofmonocarboxylic acids, e. g., vinyl acetate, vinyl propionate; theacrylic and methacrylic acids, their esters, nitriles, and amides, e.g., acrylic acid, methyl methacrylate, ethyl acrylate, acrylonitrile,methacrylonitrile, methacrylamide; the monounsaturated hydrocarbonshaving a terminal ethylenic double bond, e. g., isobutylene, and thelike. The preferred epoxy monomers are glycidyl methacrylate and allylglycidyl ether.

The most useful starting materials, because they lead toalkali-insoluble polymeric phosphates possessing the best combination ofproperties, particularly with respect to use in coating compositions,are the copolymers of glycidyl methacrylate with methacrylates ofalkanols of one to four carbon atoms, e. g., methyl, ethyl, n-propyl andn-butyl methacrylates, such copolymers containing from to 35% by weightof polymerized glycidyl methacrylate. Outstanding results are obtainedwith the alkali-insoluble polymeric phosphates derived from copolymerscontaining from to 25% by weight of polymerized glycidyl methacrylateand from 85 to 75% by weight of polymerized methacrylate of an alkanolof one to four carbon methacrylate. Thus, the preferred compounds ofthis invention are the alkaliinsoluble polymeric phosphates obtained byaction of phosphoric acid on copolymers containing from 1525% by weightof polymerized glycidyl methacrylate and 85-75% of polymerized methylmethacrylate. When these copolymers are substantially completelyphosphated by reacting them With one mole or more of phosphoric acid peroxirane oxygen the calculated phosphate content, as H2PO4, of theresulting phosphates is between 9.3 and 14.6%. Products which are evenmore satisfactory from the standpoint of use in coating compositions areobtained by partial phosphation of these copolymers, e. g., by reactingthem with 0.6-0.9 mole of phosphoric acid per oxirane oxygen.Thepolyphosphates so obtained produce coating compositions which may becured at lower substantially completely phosphated products.

When alkali-soluble polymeric phosphates are desired, preferred startingmaterials are the copolymers of allyl glycidyl ether and vinyl acetate,especially those containing between 3% and 50% by weight of polymerizedallyl glycidyl ether. Another class of polymers leading to use fulalkali-soluble polymeric phosphates are the copolymers of glycidylmethacrylate and methyl methacrylate containing from 35% to 50% byweight of polymerized glycidyl methacrylate.

As already stated, it is important to use at least about one-half moleof phosphoric acid per oxirane oxygen in the preparation of thepolymeric phosphates of this invention, since the use of smaller amountstends to cause crosslinking and gelation of the polymeric epoxide. Theupper limit is not critical since the unreacted acid can readily beremoved by washing with Water, and there may be used as much as 25moles, or even more, of phosphoric acid per oxirane oxygen. However,when alkaliinsoluble polyphosphates are to be prepared from copolymerscontaining more than about 3.9% oxirane oxygen, it is desirable to useless than one mole of phosphoric acid per oxirane oxygen. For thepreparation of alkalisoluble polyphosphate, a satisfactory range ofproportions is between 1 and 10 moles of phosphoric acid per oxirane 100C. It proceeds rather slowly at oxygen. The optimum amount will vary tosome extent in relation to the concentration of the epoxide polymer inthe reaction medium. With dilute solutions of epoxide polymers, e. g.,solutions about 10% concentration or lower, amounts of phosphoric acidas low as about one-half mole per oxirane oxygen may be used with littledanger of gelation. With more concentrated solutions of epoxidepolymers, it is desirable to use at least 1 mole of phosphoric acid peroxirane oxygen, and with concentrations in the range of 20-75% it ispreferable to use from 4 to 15 moles of phosphoric acid per oxiraneequivalent.

Orthop'hosphoric acid is the preferred phosphoric acid agent because ofits availability at low cost and of its easy reaction to give uniformproducts, but other acids of phosphorus such as metaphosphoric andpyrophosphoric acids can be used. Likewise, partially esterifiedphosphorus acids such as methyl acid phosphate or butyl acid phosphatecan be used.

In order to minimize the possibility of crosslinking of the polymericepoxide, the esterification reaction should be carried out in asolutionof the polymer in an organic solvent, which solvent should, of course,be substantially inert toward the epoxide linkages and the phosphoricacid. Such solvents are represented by the aromatic hydrocarbons, suchas benzene, toluene or the xylenes; aliphatic or aromatic ketones suchas acetone, methyl ethyl ketone, cyclobutanone, acetophenone; acyclic orcyclic ethers such as di-n-butyl ether, dioxane, tetrahydrofurane,diphenylene oxide; aliphatic alcohols such as ethanol, n-butanol,isopropanol; and the like. Preferably, the solvent is one that ismiscible with water to permit the use of aqueous solutions of phosphoricacid. The polymer solutions can be as dilute as desired, e. g., down to1% concentration by weight, but it is in general unnecessary to use aconcentration below 10%. The concentration can be as high as possible,e. g., up to 75% a preferred range being 10 to 35% by weight.

The esterification reaction can take place at a practical speed at anytemperature above 0 C. and below temperatures up to 30 C., and morerapidly at elevated temperatures up to 100 C. A particularly usefulrange of temperatures is 50 to C. Within this range the reaction is, ingeneral, substantially complete within a period of one half to threehours. It is desirable to avoid long reaction periods and hightemperatures. In other words, conditions as mild as possible aredesirable.

The reaction product, i. e., the polymeric phosphate, is preferablyisolated by adding sufficient water to the reaction mixture toprecipitate the polymer or, if the latter is water-soluble, an aqueoussolution of a salt such as sodium chloride, potassium sulfate, sodiumphosphate, etc., can be used. The polymer is then washed with water or asalt solution to remove the excess phosphoric acid. With the partiallyphosphated materials, such a separation is not necessary. A coatingcomposition may be prepared directly from the resulting solution.

The polymeric esters of phosphoric acid so obtained are resinousmaterials varying in consistency from viscous semi-solids to tough,moderately brittle, hard solids. Their molecular weights vary from about1500 to about 50,000 or higher, but are generally in the range of about2000 to about 10,000. These products are soluble in organic solvents,generally in the same solvents in which the polymeric epoxides aresoluble.

As already discussed, some of the polymeric phosphates of this inventionare soluble in dilute aqueous alkali, or even in water.Alkali-solubility appears when the calculated phosphate content is aboveabout 19% by weight as H2PO4, with the exception of the polyphosphatesderived from vinyl carboxylate/epoxy copolymers, which arealkali-soluble even at much lower phosphate contents. These highlyphosphated products are soluble in water containing sufficient alkalifor partial or complete compatible with l neutralization of thephosphoric acid groups. Such alkali may be an alkali metal hydroxide, e.g., sodium or potassium hydroxide, ammonia, or an alkylamine, preferablyone containing 1 to 6 carbon atoms, such as methylamine, n-butylamine,diethylamine, triethylamine, ethanolamine, diethanolamine,cyclohexylamine, and the like. These polymeric phosphates also formsalts with other metals such as copper, silver, zinc, aluminum, iron,nickel, cobalt, chromium or manganese. Some of these salts such as thezinc polyphosphates are insoluble in water as neutral salts but arewater-soluble as partially neutralized acid salts, and are also solublein certain organic solvents. Other salts such as the nickel and coppersalts are soluble in water when combined with excess ammonia. This ispresumably due to the formation of a metal-ammonia complex. The mostuseful of the salts are the water-soluble alkali metal, ammonium orsubstituted ammonium salts, i. e., the amine salts and particularly theammonium salts.

The most important products of this invention, however, are thosepolymeric phosphates which are insoluble in dilute aqueous alkali. Theseproducts in general have a calculated phosphate content of less thanabout 19% as -H2PO4. A phosphate content of at least 1.75%, andpreferably at least 3%, is desirable to impart useful improvements andsubstantially different properties to the polymeric phosphates incomparison with the copolymers from which they are derived, and the bestproperties are obtained when the H2PO4 content is in the range of from7% to 15%. These alkali-insoluble polyphosphates give coatings which areharder, glossier, less sensitive to water and chemicals and moreresistant to discoloration than the alkali-soluble polyphosphates.

The polymeric phosphates of this invention, and particularly thealkali-insoluble ones, are outstandingly useful as ingredients ofcoating compositions, which can be clear or pigmented. Clearcompositions can be prepared with any suitable organic solvent, such asacetone, methyl isobutyl ketone, n-butyl alcohol and the like. A widevariety of pigments commonly used in organic coating compositions can beincorporated, including titanium dioxide, carbon black, ironblues,phthalocyanine blues and greens, metal oxides and chromates, organicmaroons, and various inert extenders such as talc, barytes and chinaclay. Other film-forming materials, which are the polyphosphates of thisinvention and which are. soluble in the same solvents, may be blendedwith polyphosphate solutions to produce clear or pigmented coatingcompositions; Examples of such filmforming materials areurea-formaldehyde resins, melamine-formaldehyde resins, alkyd resins andother natural and synthetic polymers.

Two other important uses of the products of this invention have alsobeen described, these being the sizing of .fibers of the polyester type,e. g., polyethylene terephthalate, and the treatment of leather. Theyhave many other applications. For example, the already mentioned metalsalts (e. g., copper or nickel) which can be watersolubilized by meansof ammonia, may be applied to substrates from aqueous solutions. 'Onair-drying, the residual films evolve ammonia and gradually becomeinsolublein and insensitive to water. Curing at elevated temperatures,e. g., 80-l50 C., increases the rate of insolubilization. Films orcoatings of water-soluble polyphosphate salts such as those of aluminumor chromium may be prepared in situ by impregnating substrates such aspaper, textiles, wood, leather or ceramics with a water-soluble salt ofthese metals and subsequently treating the impregnated substrate with asoluble ammonium or alkali metal polyphosphate. Alternatively,'thesubstrate may be impregnated first with the soluble polyphosphate andthen treated with a suitable inorganic salt. This treatment forms theinsoluble metal polyphosphate within the pores or fibers of thesubstrate. Thus, there can be obtained coatings or films having certainspecial properties such as improved body or stiffness, increasedstability and durability, increased flame-resistance, etc.

Polyphosphate salts of metals such as copper or mercury havebactericidal and fungicidal properties and are useful asspreader-sticker or anchoring agents for insecticides,insect-repellents, herbicidal compositions and preservatives for wood ortextiles.

Some of the polymeric phosphates of this invention have excellentadhesive properties because of their good initial tackiness and the highfilm strength which develops on air-drying or curing at elevatedtemperatures. Thus, they are useful as adhesives for paper, textiles,wood, metal, plastics and other substrates of similar or differentnature.

. The wateror alkali-soluble polymeric phosphates of this invention arecompatible to a considerable extent with colloidal silica sols and suchcompositions are useful in adhesives, finishes and in dispersed systemssuch as polymer dispersions and wax dispersions.

Aqueous solutions of ammonium, amine or alkali metal polyphosphates areuseful as clear finishes for wood, glass, ceramics, textiles, paper,metals and other substrates and may be used either as primer-sealercoats for subsequent application of other finishes or as thetotalprotective or decorative finish for these substrates. Salts such ascupric ammonium polyphosphates are especially useful for sealing wood,textile and paper surfaces since the salt becomes insensitive to wateron drying and also imparts a preservative action to such cellulosicsubstrate surfaces.

Aqueous solutions of low molecular weight, soluble polyphosphates showsurface active properties and can be used as dispersing agents inpreparing oil or paint emulsions and in polymerizing ethylenicallyunsaturated compounds in aqueous systems. They are especially useful aspigment dispersing agents and pigment binders in the preparation ofwater paints and pigment printing compositions. They are also useful aslime sequestering agents, detergents and detergent assistants.

'As many apparently widely different embodiments of this invention maybe made without departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

I claim:

1.-A polymeric material selected from the class consisting of polymericphosphates and their water-soluble salts, said polymeric phosphateshaving a calculated phosphate content of at least 1.75% by weight asH2PO4, and being the reaction product of a polymeric epoxide copolymerhaving a molecular weight of at least 1500 with phosphoric acid inamount of at least one-half mole per oxira'ne oxygen atom in saidcopolymer, said polymeric epoxide copolymer having an epoxide oxygencontent within the range of 0.3 to 8% by weight and containing withinthe range of 3 to 60% by weight of a polymerized, ethylenicallyunsaturated epoxy monomer and within the range of 97 to 40% by weight ofa polymerized, acylclic ethylenically unsaturated epoxy-free.

monomer.

2. A polymeric material as set forth in claim 8 wherein said acyclicethylenically unsaturated epoxy-free monomer contains a single ethylenicdouble bond as the sole carbon-to-carbon unsaturation.

3. A polymeric material as set forth in claim 8 wherein said acyclicethylenically unsaturated epoxy-free monomer is a methacrylate of analkanol of 1 to 4 carbon atoms. I

4. A polymeric material as set forth in claim 8 wherein said acyclicethylenically unsaturated epoxy-free monomer is methyl methacrylate.

5. A polymeric material as set said acyclic ethylenically unsaturatedepoxy-free monomer is vinyl acetate.

6. A polymeric material as set forth in claim 8 wherein forth in claim 8wherein said polymeric phosphates are the reaction product of saidpolymeric epoxide copolymer with phosphoric acid in amount of at leastone mole per oxirane oxygen atom in said copolymer.

7. A polymeric material as set forth in claim 8 wherein said polymericphosphates have a calculated phosphate content within the range of 3 to19% by weight as the --H2P04. and said polymeric epoxide copolymer hasan epoxide oxygen content within the range of 0.6 to 7% by weight.

8. A polymeric phosphate having a calculated phosphate content of atleast 1.75% by weight as H2PO4, and being the reaction product of apolymeric epoxide copolymer having a molecular weight of at least 1500with phosphoric acid in amount of at least one-half mole per oxiraneoxygen atom in said copolymer, said polymeric epoxide copolymer havingan epoxide oxygen content within the range of 0.3 to 8% by weight andcontaining within the range of 3 to 60% by weight of a polymerized,ethylenically unsaturated epoxy monomer and within the range of 97 to40% by weight of a polymerized, acyclic ethylenically unsaturatedepoxy-free monomer.

9. A clear coating composition comprising a solvent and as afilm-forming material in solution therein a polymeric phosphate as setforth in claim 8.

10. A pigmented coating composition comprising a pigment, a solvent andas a film-forming material in solution therein a polymeric phosphate asset forth in claim 8.

11. A polymeric phosphate having a calculated phosphate content of atleast 1.75 by weight as -H2PO4, and being the reaction product of apolymeric epoxide copolymer having a molecular weight of at least 1500with phosphoric acid in amount of at least one-half mole per oxiraneoxygen atom in said copolymer, said polymeric epoxide copolymer havingan epoxide oxygen content within the range of 0.3 to 8% by weight andcontaining within the range of 3 to 60% by weight of polymerizedglycidyl methacrylate and within the range of 97 to 40% by weight of apolymerized, acyclic vinylidene epoxy-free monomer containing a singleethylenic double bond as the sole carbon-to-carbon unsaturation.

12. A polymeric phosphate having a calculated phosphate content of atleast 1.75% by weight as H2PO4, and being the reaction product of apolymeric epoxide copolymer having a molecular weight of at least 1500with phosphoric acid in amount of at least one-half mole per oxiraneoxygen atom in said copolymer, said polymeric epoxide copolymer havingan epoxide oxygen content within the range of 0.3 to 8% by weight andcontaining within the range of 3 to 60% by weight of polymerized allylglycidyl ether and within the range of 97 to 40% by weight of apolymerized, acyclic vinylidene epoxy-free monomer containing a singleethylenic double bond as the sole carbon-to-carbon unsaturation.

13. A polymeric phosphate having a calculated phosphate content of atleast 3% by weight as -H2PO4, and being the reaction product of apolymeric epoxide copolymer having a molecular weight of at least 1500with phosphoric acid in amount of at least one-half mole per oxiraneoxygen atom in said copolymer, said polymeric epoxide copolymer havingan epoxide oxygen content within the range of 0.3 to 8% by weight andcontaining within the range of 3 to 60% by weight of allyl glycidylether and within the range of 97 to 40% by weight of vinyl acetate.

14. A polymeric phosphate having a calculated phosphate content withinthe range of 3 to 19% by weight as -H2PO4, and being the reactionproduct of a polymeric epoxide copolymer having a molecular weight of atleast 1500 with phosphoric acid in amount of at least one-half mole peroxirane oxygen atom in said copolymer, said polymeric epoxide copolymerhaving an epoxide oxygen content Within the range of 0.6 to 3.9% byweight and containing within the range of 5 to 35% by weight ofpolymerized glycidyl methacrylate and within the range of 95 to byweight of a polymerized methacrylate of an alkanol of l to 4 carbonatoms.

15. A polymeric phosphate as set forth in claim 14 wherein saidpolymerized methacrylate of an alkanol of 1 to 4 carbon atoms ispolymerized methyl methacrylate.

16. A polymeric phosphate having a calculated phosphate content of atleast 1.75% by weight as -H2PO4, and containing epoxy groups unreactedwith phosphoric acid, and being the reaction product of a polymericepoxide copolymer having a molecular weight of at least 1500 withphosphoric acid in amount of at least one-half mole per oxirane oxygenatom in said copolymer, said polymeric epoxide copolymer having anepoxide oxygen content within the range of 0.3 to 8% by weight andcontaining within the range of 3 to 60% by Weight of a polymerized,ethylenically unsaturated epoxy monomer and Within the range of 97 to40% by weight of a poly merized, acyclic ethylenically unsaturatedepoxy-free monomer.

17. A polymeric phosphate having a calculated phos phate content ofabove 19% by weight as H2PO4, and being the reaction product of apolymeric epoxide copolymer having a molecular Weight of at least 1500with phosphoric acid in amount of at least one-half mole per oxiraneoxygen atom in said copolymer, said polymeric epoxide copolymer havingan epoxide oxygen con tent within the range of 3.9 to 7% by Weight andcontaining within the range of 3 to 60% by weight of a polymerized,ethylenically unsaturated epoxy monomer and within the range of 97 to40% by weight of a polymerized, acyclic ethylenically unsaturatedepoxy-free monomer.

18. A polymeric phosphate having a calculated phosphate content of above19% by weight as H2PO4, and being the reaction product of a polymericepoxide copolymer having a molecular weight of at least 1500 withphosphoric acid in amount of at least one-half mole per oxirane oxygenatom in said copolymer, said polymeric epoxide copolymer having anepoxide oxygen content Within the range of 3.9 to 8% by weight andcontaining within the range of 3 to 60% by weight of allyl glycidylether and within the range of 97 to 40% by weight of vinyl acetate.

19. A polymeric phosphate as set forth in claim 11 wherein said acyclicvinylidene epoxy-free monomer is methyl methacrylate.

20. A polymeric phosphate as set forth in claim 11 wherein saidpolymeric phosphate is the reaction product of said polymeric epoxidecopolymer with phosphoric acid in amount of at least one mole peroxirane oxygen atom in said copolymer and said acrylic vinylideneepoxy-free monomer is methyl methacrylate.

References Cited in the file of this patent UNITED STATES PATENTS

1. A POLYMERIC MATERIAL SELECTED FROM THE CLASS CONSISTING OF POLYMERICPHOSPHATES AND THEIR WATER-SOLUBLE SALTS, SAID POLYMERIC PHOSPHATESHAVING A CALCULATED PHOSPHATE CONTENT OF AT LEAST 1.75% BY WEIGHTAS-H2PO4, AND BEING THE REACTION PRODUCT OF A POLYMERIC EPOXIDECOPOLYMER HAVING A MOLECULAR WEIGHT OF A T LEAST 1500 WITH PHOSPHORICACID IN AMOUNT OF AT LEAST ONE-HALF MOLE PER OXIRANE OXYGEN ATOM IN SAIDCOPOLYMER, SAID POLYMERIC EPOXIDE COPOLYMER HAVING AN EPOXIDE OXYGENCONTENT WITHIN THE RANGE OF 0.3 TO 8% BY WEIGHT AND CONTAINING WITHINTHE RANGE OF 3 TO 60% BY WEIGHT OF A POLYMERIZED, ETHYLENICALLYUNSATURATED EPOXY MONOMER AND WITHIN THE RANGE OF 97 TO 40% BY WEIGHT OFA POLYMERIZED ACYLCLIC ETHYLENICALLY UNSATURATED EPOXY-FREE MONOMER.